DE1768441C - Process for the preparation of aldehydes and alcohols after the oxo synthesis - Google Patents

Description

1 2

The invention relates to a method for using tributylphosphine as when using

Production of aldehydes and alcohols according to the modified catalysts.

Oxo processes by reacting olefinically unsuitable aliphatic, cycloaliphatic are preferred

saturated compounds with carbon monoxide and / or araliphatic olefinically unsaturated compounds

Hydrogen in the presence of carbonyl complexes 5 gene with 2 to 20 carbon atoms, especially with

of metals of group VIII of the periodic 2 to 16 carbon atoms. The prefer-

System that can be modified by substituted phosphines th olefinically unsaturated compounds

are. several double bonds, e.g. B. two unconjugated

A method generally introduced in the art of double bonds or under reaction conditions for the preparation of aldehydes and alcohols is d >> \ o inert substituents, such as alkoxy groups with 1 to oxo synthesis, in which olefins with carbon _{mono A} ia 4 carbon atoms, carboxyl groups, carbalkoxy and hydrogen in The presence of cobalt carbonyl groups with 2 to 9 carbon atoms or nitrile compounds are implemented as a catalyst. Have groups. Particularly preferred are olefinic processes, which have the disadvantage that up to a certain extent, unsaturated compounds containing carbon atoms, branched aldehydes and alcohols which have less structure, are used as starting materials. Are desired, arise. Olefins are also known to have a special technical importance with 2 to 4 processes in which a higher 20, especially with 2 to 16 carbon atoms, especially those with terminal double bonds, of straight-chain aldehydes and alcohols are obtained. Thus, in British Patent Specification 903,598 is obtained. Suitable olefinically unsaturated compounds that one obtains a higher proportion of opposite genes are, for example, ethylene, propylene, 1-hexene, chain compounds when the 1-oxo-octene, 1-decene, cyclohexene, styrene, propenylbenzene react Temperatures of 110 to 130 ^c C through allyl alcohol, allyl methyl ether, crotonic acid methyl leads. The disadvantage, however, is that only relatively low conversions are achieved in the case of lower tertiary esters, ethyl acrylate, acrylonitrile, olefin mixtures. as in the oligomerization of propene and butene

According to another known process (French 35 incurred, e.g. so-called trimer propylene or

French Patent 1,374,941) is obtained by codibutylene.

Use of high pressures, e.g. B. 500 to 1200 At- carbon monoxide and hydrogen are generally

atmospheres, a higher proportion of straight-chain mine in a volume ratio of 1: 1 to 10,

Oxygenation products. The use of such high pressures, especially in a ratio of 1: 1 to 3,

however, requires a disproportionately large 30 used.

technical effort. Furthermore, from the USA.- It is possible, the olefinically unsaturated Verbin-Patentschfift 2 694 735 known that the oxo reaction fertilize in stoichiometric amounts, based on propylene in favor of the formation of straight-chain products, the mixture of carbon monoxide and hydrogen if you can use the to-. However, it is advantageous to use the setting in the presence of ketones. Called this 35? However, the stoichiometric gas mixture requires an additional shot during work-up. However, it is also possible to have more than one stage for the recovery of the ketones. In the documents of the Dutch mixture published on the stoichiometric excess of the gas, e.g. B. to use up to 500 ° / ₀ .
Patent application 6 400 701 and the German version of the implementation is carried out with advantage in Temperalegeschrift 1186 455 is also already described, 40 doors from 140 to 250 ⁰ C through. Particularly good results are obtained by using in the oxo reaction when temperatures of carbonyls of metals of Group VIII of 170 to 230 ° C. are used. Good results are obtained from the Periodic System, which is carried out with phosphines, arsines, if the reaction is modified by pressures or stibines, predominantly in straight-chain 30 to 350 atmospheres. It is advantageous to use oxo reaction products. Finally, the 45 man pressures from 60 to 300 atmospheres.
known documents of the Dutch It is possible to carry out the implementation without additional patent applications 6 516164 and 6 604 094 also using solvents. The already phosphines, in which the phosphine group is part of the olefinically unsaturated compounds of a heterocyclic ring used, serve as modifiers in this case as solvents. Other means for oxo reaction catalysts described on the other hand, however, it is also possible under reaction. All previously known phosphines containing inert solvents, such as carbon oxo reaction catalysts, however, have the post-hydrogen, for example cyclohexane or xylene, part that in their presence the oxo reaction is slower and alcohols, such as butanol or aldehydes, as is the case with the cobalt previously used - Butyraldehyde, to be used as a solvent. In carbonyl catalysts that are not modified. 55 of the technology, one uses appropriately the as

It has now been found that aldehydes and reaction products can be used as a solution

Alcoholc after the oxo synthesis by conversion of medium.

olefinically unsaturated compounds with carbon The reaction is carried out in the presence of carbonyl

monoxide and hydrogen at elevated temperature complex of metals of the VIII, group of

and under increased pressure in the presence of Carbo * 60 Periodic Table, by Phosphamorpholine

nylon complexes of metals of the VHi. Group of are substituted, performed. Preferred carbonyl

Perindian system, which is characterized by trtsubstituierle phos- complexes of metals of the VHL group of the Perio-

phinc are modified, obtained more advantageously than hitherto, Jisch'n systems are those of Bisen, Cobalt,

If the modifier is phosphamorpho-rhodium or palladium, particularly good results

line used. 65 is obtained with cobalt and Rhodiumcarbonylkonv

The new process has the advantage that one plexes, especially cobalt carbonyl complexes, Be *

predominantly gcradkctligs oxo reaction products are obtained, preferred catalysts contain metal and phosphorus

■■ ml of iiiiflL-rrium. (litli das Verfuhren rüscher runs in an atomic ratio of 1: 1 to 4, especially in the

Claims (1)

3 4 Ratio 1: 1 to 2. It is also possible to add 20 g of cobalt ethyl hexanoate (85 in addition to the reaction mixture, the stated phospha weight percent) and 29.2 g of dodecylphosphamorpho- add morpholine. lin (95 percent by weight) contains. Dosed at the same time As a modifier, phosphamorphomans from below become so much of a mixture of carbon lines used. Preferred phosphamorpholines are 5 monoxide and hydrogen in a volume ratio of 1: 2 to, those of the formula that maintain a pressure of 80 atmospheres R becomes, while the reaction is carried out at 190 ⁰ C 1 "leads. 68.8 parts of a red per hour are obtained ^/ "' ^v Discharge from the refractive index n" = 1.4268. One ^ i P O ίο sample of the discharge shows in the infrared spectrum, a - strong band at 1950 cm " ^1. This comes from the in the R ₁ an aliphatic, cycloaliphatic ^ complex of cobalt, carbon monoxide and dodecyl araliphatic or aromatic radical with 6 to phosphamorpholine. According to gas chromatography 2 carbon atoms. Analysis of the residues does not contain 18 percent by weight of the discharge Substituents inert under reaction conditions, 15 converted octene (l), 10 percent by weight octane, such as hydroxyl or alkoxy groups having 1 to 4 carbon 2 ° / ₀ nonanals and 66.5 ° / "nonanols, 86 ° / ₀ of erzeug- have material atoms. R, means a water coff atom ten nonanols are nonanol {1).
or a lower alkyl radical, especially one Alkyl radical with 1 to 4 carbon atoms, and η is comparative example 1 for an integer from 0 to 4. Particularly preferably 20 are phosphamorpholines of the above formula, the procedure is as described in Example 1, in which R _{1 is} an alkyl radical with 6 to 20 carbon but uses octene (l), which per kilogram 20 g atoms and R ₁₈ for a hydrogen atom cobalt ethyl hexanoate (85 weight percent) and 20.2 g and η means the number 4. Suitable phospha- tri-n-butylphosphine contains as a starting material. Man morpholines are z. B. p-Dodecylphosphamorpholine, 25 receives hourly 67 parts of a mixture that according to p-TetradecylpMsphamorpholine, p-Octadecylphospha- gas chromatographic analysis 22.5 percent by weight morphcline, p-cyclohexylphosphamorpholine, p-benzyl- cent unreacted octene (l), 10 percent by weight phosphamorpholine, p-pnenylp: <osphamorpholine. Octane, 2.5 percent by weight nonanals and 56 Ge It is advantageous to use the catalysts containing nonanols by weight Amounts from 0.1 to 2 percent by weight, calculated as the conversion of octene (l) and the yield of Metal, based on the olefins used. Nonanols per unit of time is therefore much lower Particularly good results are obtained if, as in Example 1.
0.2 to 1 weight percent used. It is possible, prepare the catalysts before the reaction, comparative example 2 on the other hand it is also possible to use the catalysts in 35 situ during the reaction from the individual constituents - You proceed as described in Example 1, share, e.g. B. fatty acid salts of metals and used, however, octene (l), which per kilogram 20 g to produce specified phosphamorpholines. Cobalt-2-ethyl-hexanoate and 21.7 g of dibutyl- (2-pyri- The method according to the invention carries out one containing dyl) phosphine. 69 parts per hour are obtained, for example, by adding octene (l), a mixture of carbon monoxide, octene (l), a mixture of carbon monoxide, to a vertical 40% of an oxo reaction mixture, which, after a high-pressure tube is gas-chromatographed from below in the given graphic analysis, has a 13.1 percent by weight non-ratio of olefins 6.0 percent by weight octane, 4.0 percent by weight and hydrogen and catalyst, optionally percent by weight nonalals and 55.4 percent by weight together with a suitable solvent, to nonalols. Results in only 55 ° / ₀ of Nonalole formed and under the stated pressure and temperature are Nonanol- 45 (l). In addition, the reaction continues under the distillation conditions. The tion of the oxo reaction mixture a residue of reaction mixture is released after releasing z. B. 19.7 percent by weight of high-boiling parts,
freed from the catalyst by distillation and
then broken down into the individual components according to known methods. E3 is possible, but not the other way round.
exposed olefins or unconsumed mixture
Carbon monoxide and hydrogen restart the reaction
to feed. Process for the preparation of aldehydes and The alcohols prepared by the process of the invention after the oxo synthesis by reaction Aldehydes and alcohols are suitable for the production of olefinically unsaturated compounds of solvents and plasticizers for polymers. Carbon monoxide and hydrogen at elevated levels The »parts of temperature and under increased pressure given in the following examples in counter- are parts by weight. They relate to the space wart of carbonyl complexes of metals divide as kilograms to liters. VIII. Group of the Periodic Table, by . 60 trisubstituted phosphines are modified, d a- For example, characterized by that as Use modifier phosphamorpholine in a high pressure vessel of 500 room dividers. 58 parts of octene (1) are added every hour from below.